I-nh-so



United States Patent Ofiice Patented July 17, 1962 This inventionrelates to new chromium and cobalt complex dyestuffs free from sulfonicacid groups. More particularly it relates to chromium and cobalt complexdyestuits free from sulfonic acid groups which contain two identical azodyestufi radicalsattached to one chromium or cobalt atom.

It is known that wool can be dyed with good wet fastness properties withmetal complex dyestufis which do not contain free sulfonic acid or freecarboxylic groups but contain sulfonic acid amide or carboxylic acidamide groups which bear on the nitrogen atom non-ionogenic substituents.It is also known that the wet fastness properties of such dyeings arehigher the greater the molecular weights of the said non-ionogenicsubstituents are. As

experts known, the leveling power of the metal complex dyestutis on theother hand declines as the molecular weight of the said non-ionogenicsubstituents increases, so that it is often ditficult to produce dyeingson wool which have excellent wet fastness properties and at the sametime are level.

It is an object of the present invention to provide metal complexdyestuffs with which wool can be dyed with excellent wet fastnessproperties and at the same time excellent levelness.

The new dyestufis are chromium and cobalt complexes in which to onechromium or cobalt atom there are attached two identical azo dyestufr'radicals which are free from sulfonic acid groups but are substituted atthe diazo or at the coupling component by the radical CHgOH2 CH2C./H2which radical is linked to the said components either directly or by wayof one or more atoms forming a group of the type specified below. The.diazo component is a benzene nucleus substituted by :an azo group, acomplex forming group attached to the benzene nucleus in orthopositionto the azo group, and if desired by neutral substituents of the typespecified below. The coupling component is a benzene, a naphthalene oran enolic compound capable of coupling, each of them containing acomplex forming group attached in ortho-position to the coupling carbonatom if it is an aromatic and in alpha-position if it is an enoliccompound. The dyestuffs can be illustrated by the general formula and inwhich L is a hydrogen atom, a chlorine atom, an acetylamino group or amethoxycarbamino group, G a hydrogen atom, a methyl group or a chlorineatom, Q a hydrogen atom or a chlorine atom, and the group is attached toan aromatic nucleus of the azo dyestuif radical. The asterisk indicatesthe position in which the above components are coupled to the azo groupin the dyestutf structure, the remaining bond connecting the adjacentcarbon atom through the divalent radical Y to the metal atom M.

The new chromium and cobalt complex dyestuffs are obtained by treatingazo dyestuifs of the general formula:

a in which B, R R X, Y and Z have the meanings given above and A standsfor a hydrogen atom or a methyl group, in aqueous solution or suspensionor in an organic solvent or in a mixture of water and an organic solventmiscible with water, at elevated temperature with an agent yieldingchromium or cobalt. Suitable organic solvents miscible with waterinclude dimethylformamide and di- Z-hydroxyethyl) -ether.

Agents yielding chromium or cobalt which can be used for this purposeinclude sodium dichromate, potassium dichromate, ammonium dichromate,chromiumflll) chloride hexahydrate, chromium(III) formate and cobalt(II)chloride hexahydrate.

The azo dyestuffs of the above Formula H can be prepared by diazotizingamines of the benzene series of the general formula:

in which R R X, A. and Z have the meanings given above and p is 1 or 2and reacting them with coupling components of the general formula:

in which E, Y, Z and p have the meanings given above.

Diazo components containing the group in the molecule which are suitablefor the preparation of the azo dyestuffs of Formula II are for exampleN-(lamino 2 hydroxybenzenesulfonyl), N (1 amino-2-methoxybenzenesulfonyl), N-(l-amino 2 carboxybenzenesulfonyl),N-(l-amino 2 hydroxybenzoyl) and N- (l-amino 2 methoxybenzoyl)derivatives of l-aza-4- thiacyclohexane-4,4-dioxide.

As coupling components which bear the group there are suitable forexample the N-(acetoacetylaminobenzenesulfonyl),N-(acetoacetylamino-benzoyl), N-([3- methylpyrazol 5 one 1yll-benzenesulfonyl), N-( [3- methylpyrazol 5 one 1 yl]-benzoyl),N-(hydroxybenzenesulfonyl) and N-(hydroxybenzoyl) derivatives ofl-aza-4-thiacyclohexane 4,4 dioxide and thoseN-(hydroxynaphthalenesulfonyl) N- (hydroxynaphthoyl) N-(aminonaphthalenesulfonyl) and N-(aminonaphthoyl) derivatives of1-aza-4-thiacyclohexane-4,4-dioxide which permit coupling inortho-position to the hydroxy or amino group.

These components can be obtained by reacting the corresponding sulfonicor carboxylic acid halides in aqueous suspension or in organic solventsin the presence of acidbinding agents with1-aza-4-thiacyclohexane-4,4-dioxide and then producing the amino orhydroxyl groups necessary for diazotization or coupling in the reactionproducts, if they are not already present, by reduction orsaponification. The dyestutf primary products may also contain theabove-mentioned substituents, such as halogen atoms, and/ or alkyl,alkoxy, nitro and/or acylamino groups.

Further suitable diazo components which contain the radical of1-aza4-thiacyclohexane-4,4-dioxide are for ex- 4 ample the N-(l-amino 2hydroxybenzenesulfonyl), N- (l-amino 2 methoxybenzenesulfonyl),N-(l-amino-Z- carboxybenzenesulfonyl), N-(l-amino 2 hydroxybenzoyl) andN-(1-amino-2-methoxybenzoyl) derivatives of the amines or hydrazines ofTable 1:

The production of 1-aza-4-thiacyclohexane4,4-dioxide and of the amines 1to 4 of Table 1 is described in the copending patent application SerialNo. 828,048, filed July 20, 1959, by Robert Gehm and Johannes Dehnert.

The amine 5 may be obtained for example by reaction of 4-nitrobenzylchloride with l-aza-4'thiacyclohexane- 4,4-dioxide and reduction of the1-(4-nitrobenzyl)-l-aza- 4-thiacyclohexane-4,4-dioxide formed.

The acid amides containing the radical of1-aza4-thiacyclohexane-4,4-dioxide can be prepared, using the amines ofTable l, by the usual methods known for the production of substitutedamides of these acids. A further substance suitable for the productionof the new dyestuffs is for example l-carboxymethyl-l-aza 4thiacyclohexane- 4,4-dioxide, the production of which is described inthe Journal of the Chemical Society, London, volume 123, page 2888.

By reaction of l-hydroXy-2-amino-4,6-dinitrobenzene with the carboxylicacid chloride of l-carboxymethyl-laza-4-thiacyclohexane-4,4-dioxide andpartial reduction of the reaction product there is obtained for examplethe diazo component of the formula:

I NH-CO-CHr-N SO:

By coupling the diazotized amine 5 of Table 1 with ahydroxynaphthalenesulfonic acid which couples in orthoposition to thehydroxy group, oxidative coppering of the resultant azo compoundaccording to the process of US. patent specification No. 2,674,595 andreductive splitting off of the copper complex, it is possible forexample to prepare the diazo component of the formula:

Suitable coupling components which contain the radical ofl-aza-thiacyclohexane 4,4 dioxide include the N-(acetoacetylaminobenzenesulfonyl), N-( [3 methylpyrazol 5 one 1yl]-benzenesulfonyl), N-([3-methylpyrazol 5 one 1 yIJ-benzoyl),N-(hydroxybenzoyl),

N-(hydroxybenzenesulfonyl) derivatives of the amines of Table 1 andthose N-(hydroxynaphthalenesulfonyl), N- (hydroxynaphthoyl),N-(aminonaphthalenesulfonyl) and N-(aminonaphthoyl) derivatives of theamines of Table l which permit coupling in ortho-position to the hydroxyor amino group. These compounds can be prepared by known methods.

Further coupling components which may be used for the production of thenew dyestuffs are given in Table 2:

a sulfonic acid amide or carboxylic acid amide group which hasnon-ionogenic substituents attached to the nitrogen atom and in whichthe said substituted sulfonic acid amide or carboxylic acid amide grouphas about the same molecular weight as the group they give on wooldyeings of considerably better levelness and of wet fastness propertieswhich are at least as good. I

The following examples will further illustrate this 1nvention but theinvention is not restricted to these examples. The parts are parts byweight.

Example 1 36 parts of1-(3-acetylamino-4-methoxybenzenesulfonyl)-l-aza-4-thiacyclohexane-4,4-dioxideare boiled for an hour under reflux with 75 parts of concentratedhydrochloric acid and 500 parts of water to saponify the acetylaminogroup. The amine hydrochloride is diazotized with 30 parts of a 23%aqueous sodium nitrite solution while cooling with ice and coupled with15 parts of 2 hydroxynaphthalene dissolved in 250 parts of 2% causticsoda solution with the addition of parts of sodium carbonate and 250parts of ice. The dyestutf formed is filtered off by suction, washedwith water and dried.

For the preparation of the 1:2-cobalt complex, the metal-free dyestufli'is reacted with a solution of 13 parts of crystallized cobalt chlorideand 20 parts of 25% aqueous ammonia in 500 parts of di-(Z-hydroxyethyl)ether at 130 to 135 C., until the metallization is complete. The cobaltcomplex is isolated by introducing the reaction mixture into a solutionof 500 parts of sodium chloride in 5000 parts of water, filtration bysuction and drying of the reaction product; the dyestutf is'obtained asa dark red-brown powder which dissolves in hot water with a bluish redcolor.

100 parts of polycaprolactam fibers are introduced into a bathcontaining in 2000 parts of water, 1 part of the said cobalt complex, 4parts of 25% aqueous ammonia, 1 part of di-(hydroxyethyl)-amine and 1part of the sodium salt of a sulfonated adduct of 30 mols of ethyleneoxide and 1 mol of octadecyl alcohol, the bath heated for 30 minutes atboiling temperature, then 4 parts of ammonium sulfate are added anddyeing continued for another 30 minutes at a bath temperature of 98 to100 C. After rinsing the fabric, a Bourdeaux dyeing of excellentfastness properties and excellent levelne'ss is obtained.

For the production of the corresponding 1:2-chrornium complex compound,the dry metal-free dyestuff is stirred at C. with 500 parts ofdi-(Z-hydroxyethyl) ether. In the course of an hour, a solution of 10parts of sodium bichromate in 100 parts of di-(Z-hydroxyethyl) ether isallowed to flow in and the mixture is stirred at to C. until the initialdyestutf can no longer be detected by paper chromatographic methods. Themixture resulting from the chroming is introduced into 5000 parts ofwater and 500 parts of sodium chloride are added. The dyestuff, afterfiltration by suction, is washed with a little water and dried. It formsa dark violet-brown powder which dissolves in water with a red-violetcolor and gives on wool uniform and fast brownviolet dyeings from aneutral to weakly acid bath.

7 Example 2 12.3 parts of 2-methoxy-1-aminobenzene are diazotized in theusual way and coupled with a solution of 35 parts ofl-(6-hydroxynaphthalene-Z-sulfonyl)-1-aza-4-thiacyclohexane-4,4-dioxidein 250 parts of 2% caustic soda solution, with the addition of 50 partsof sodium carbonate and 250 parts of ice, and the resultant red dyestuffreacted with 13 parts of cobalt( III) chloride hexahydrate as describedin Example 1. The reaction mixture is introduced into 5000 parts ofwater and the deposited dyestuff is filtered off by suction, washed anddried. ilt forms a red-brown powder which dissolves in Water with a darkred color.

100 parts of wool yarn are introduced into a bath consisting of 3000parts of Water, 2 parts of the said cobalt complex, 2 parts of thesodium salt of a sulfonated adduct of 80 mols of ethylene oxide and 1mol of octadecyl alcohol, 5 parts of ammonium acetate and 3 parts of 30%aqueous acetic acid. The bath is heated to 100 C. within 30 minutes andthis temperature maintained for another 20 minutes. After rinsing, avery level, extremely fast yellowish-Bordeaux dyeing is obtained.

The corresponding 1:2-chromium complex, prepared as described in thethird paragraph of Example 1, gives on wool red-violet dyeings ofsimilar properties.

The following dyestuffs are prepared in a similar manner:

and then a solution of 13 parts of cobalt(II) chloride hexahydrate in100 parts of water is added. The whole is heated to 60 to 70 C. and thistemperature maintained until metal-free azo dyestuff is no longerdetect- Shade of dying on wool Exalglple Diazo component Couplingcomponent lz2-cobalt 1:2chrocomplex miumcomplex 31-(-methyl-4-amino-5-metl1oxy-benzene- 2-hydr0xyuaphthalenered-violet--- blue-violet.

sulfonyD-l-aza-4thiacyelo-hexane-4,4- dioxide. 41-(2-methy1-4amino-5-methoxy-benzene- I-phenyl-S-methyl-pyrazolone-(5)yellowred.

siuliotayl)-1-aza-4-thiacyclo-hexane-4,4- brown.

ioxit e. 5 1-(2,5-dirnethoxyA-aminobenzene- 2-hydroxynaphthalene violetblue.

sdlllllonlyl)-1-aza-4-thiacyclohexane-4,4-

on e. 6 1-(2,5-dimethoxy-4-aminobenzeneS-methylamino-Z-hydroxynaphthalene... blue green-blue.

sulionyl)-1-aza-4-thiaeyelohexaue-4,4- dioxide. 7l-amino-2-methoxy-achlorbenzene 1-(6-l1ydrexy-naphthalene-Z-sullonyD-l-Bordeaux... violet.

aza-4-thiacyelo-hexaneAA-dioxide. 8 1-amino-2,5-di-methoxybenzene1-(ii-hydroxy-naphthalene-ZsulfonyD-lviolet blue.

aza-tthiacyelo-hexane-4,4-dioxide. 91-(3-amino-4-methoxybenzoyll-l-azai- 2-hydroxynaphthaleneBordeauxbrownthiaeyclo-hexauel,4-dioxide. violet.

Example 10 30.6 parts of l-(3-amino-4-hydroxybenzenesulfonyl)-l-aza-4-thiacyclohexane-4,4-dioxide are dissolved in 300 parts of normalhydrochloric acid and diazotized at 0 to 5 C. with parts of 23% sodiumnitrite solution. The diazo compound obtained is coupled with a solutionof 22 parts of 8-methylcarbamino-Z-hydroxynaphthalene in 400 parts of 1%caustic soda solution with an addition of 250 parts of ice and parts ofsodium carbonate. The violet dyestuff formed is filtered off by suctionand washed with dilute sodium chloride solution.

For conversion into the cobalt complex, the metal-free dyestutr' isstirred as a moist paste with 200 parts of water able. After cooling,the complex dyestufi formed is filtered off by suction, washed with alittle water and dried. It is a dark brown powder which dissolves in hotwater with a violet color and dyes Wool from a neutral to weak acid bathin fast violet shades.

If the metal-free azo dyestuff is converted as a dry powder into itschromium complex by the process according to US. patent specificationNo. 2,230,686, Example l, a blue-grey powder is obtained which dyes woolfrom a neutral to weak acid bath in fast bluegrey shades.

The following dyestuffs can be prepared in a similar manner:

Shade of dyeing on wool of- Example No. Diuzo component Couplingcomponent 1:2- 1:2- cobaltchromiumcomplex complex H-N 11l-aminobenzeue-Q-earboxylic acid HO yellow,

C-N S Or-N S O 2 5H $11: /CHN 12 l-amino-2-hydroxy-5-nitrobenzene HOyellow orange.

CN S Or-N S 0:

l 0 H i /CHN l3 1-amino-2-hydroxy-3-nitro-5-methylbenzene. HO r d,

CN S O r-N S 0 a I L 0 H $11: /0 H-N 14l-amino-2,4-dichlorbenzene-G-carboxyllc acid.. HG yellow.

CN SO7N S O 3 I U 0 H 15 1-(4 amino 5 hydroxy benzenesulfonyl) 1-Lphenyl-3-methyl-pyrazo1one-(5) yellowscarlet,

aza--tliiacyelohexaneitdioxide. brown.

Shade of dyeing on wool of- Example No. Diazo component Couplingcomponent 1 1 2 :2- cobaltchromiumcomplex complex 16 1-(4 amino5hydr0x-ybenzenesullony1)- l-aza- 2-hydroxynaph h 'fl red-violet---blue-vilet.

4-thiacyclohexanetA-dioxide. 17 1-amin0-2-hydroxy-4-nitrobenzene 1 (6ammonaphthalene 2 sulfonyl) 1 aza 4 thiablue cyclohexaneAA-dmxide. 18 1(3 amino 4 hydroxybenzenesulfonyl) 11-(4-chl0rophcnyD-3-methylpyrazolone-(5) yellow orange,

aza-4-thiacyc1ohexane-4,4-dioxide.

HN-C O-N S 2 A 19 1-amino-2hydroxy-3-aeetylamino-5-nitrobenzenet HOOQgrey olive.

HN-C O-fi S 03 20 1-amino-2-hydroxy-5-nitrobenzene H0O do Do.

21 1-amino-2,5-dieth0xy-benzene 1- (3- hydr0xynaphtha1ene-2- sulfonyl)1- MM -thiaviolet blue.

cycl0hexane-4,4-diox1de. 22 1 (3 carboxy 4 amino benzenesulfonyl)- 1- 1-(2-methylpheny1)-3-methylpyrazo10neyellow.

aza-4-thiacyclohexane4,4dioxide.

m HNS OzN S 02 L 23 1-amino-2-hydroxy-5-nitrobenzenc H0O grey olive.

24 1- (3 amino 4 hydroxy benzenesulfonyl) 1-8-acetylamino-2-hydroxynaphthalene violet blue-grey,

aza-4thiacyclohexane4,4-dioxide.

Example 25 42 parts of the compound of the formula 02SN-CHz-CHz-CHrNH-SOz- OCHa are boiled for an hour under reflux with 75parts of concentrated hydrochloric acid and 500 parts of water tosaponify the acetylamino group. The amine hydrochloride is diazotizedwith ice cooling with 30 parts of a 23% aqueous sodium nitrite solutionand coupled with parts of 2-hydroxynaphthalene dissolved in 250 parts of2% aqueous sodium hydroxide solution with the addition of 100 parts ofsodium carbonate and 250 parts of ice. The dyestuif formed is filteredoff by suction, washed with water and reacted with a solution of 13parts of crystallized cobalt chloride and parts of aqueous ammonia in500 parts of di-(Z-hydroxyethyl) ether at 130 to 135 C. until the cobaltcomplex of the dyestufi has been completely formed. After the reactionmixture has been introduced into a solution of 500 parts of sodiumchloride in 5000 parts of Water, filtration and drying, the cobaltcomplex is obtained as a dark redbrown powder which dissolves in hotwater with a bluishred color and dyes wool and polyarnide fibersBordeaux shades which are very level and fast.

For the preparation of the 1:2-chromium complex compound, the drymetal-free azo dyestuff is stirred at 125 C. with 500 parts ofdi-(Z-hydroxyethyl) ether. In the course of an hour a solution of 10parts of sodium dichromate in 100 parts of di-(Z-hydroxyethyl) ether isadded and the whole stirred at to C. until initial dyestutf can nolonger be detected by paper chromatographic methods. The chroming mixingis intro duced into 5000 parts of Water and 500 parts of sodium chlorideare added. The dyestuif is filtered 0E by suction, washed with a littleWater and dried. It is a dark violet-brown powder which dissolves inwater with a redviolet color and dyes wool very level and fast'brownviolet shades from a neutral to weak acid bath.

Example 26 12.3 parts of Z-methoxy-l-arrfinobenzene are diazotized inthe usual way and coupled with a solution of 40 parts of the compound ofthe formula:

023 N-CH -CH -NH-SOP in 250 parts of 2% aqueous sodium hydroxidesolution with the addition of 50 parts of sodium carbonate and 250 partsof ice, and the red dyestufi obtained is reacted in the way described inExample 24, paragraph 2, with 13 parts of cobalt (II) chloridehexahydrate. The reaction mixture is introduced into 5000 parts of Waterand the deposited dyestuff filtered off by suction, washed and dried. Itis a brown-red powder which dissolves in water with a dark red color andgives on wool from a neutral to weak acid bath very level and fastdyeings in yellowish Bordeaux shades. The corresponding 1:2-chromiumcomplex, prepared as in Example 25, gives redviolet dyeings of similarproperties.

Example 36 35 parts of the compound of the formula:

with 200 parts of water and then a solution of 13 parts of cobalt(II)chloride hexahydrate added. After heating to 60 to 70 C., parts of 25%aqueous ammonia are added. The temperature of the reaction mixture ismaintained at to C. until metal-free azo dyestuff is no longerdetectable by paper chromatographic methods. After cooling, the complexdyestufi formed is filtered oif by suction, washed with a little waterand dried. It is a dark brown powder which dissolves in hot water with aviolet color and dyes wool fast violet shades from a neutral to Weakacid bath.

If the metal-free azo dyestufl as a dry powder is converted into itschromium complex by the process according to US. patent specificationNo. 2,230,686, a blue-grey powder is obtained Which dyes Wool fastblue-grey shades from a neutral to weak acid bath.

The following dyestuffs may be prepared in a similar fashion:

ample Diazo component Shade of dyeing on Wool of:

Coupling component 1:2-o0balt complex 1 2- ehrom ium complex NH: v

COOH

OzN

| I CAN OH COOH 42 01S N-SO:

OzN

NH: 02S

| o-rrQorm-rr so; OH 5H L1 HsC I yellow yelloworange.

yellowred.

brown.

yellow.

yellow grey olive.

Shade of the dyeing E. on Wool of theampl t t N o. Dlazo componentCoupling component 1:2-cobnlt 1:2-chrocomplex rnium complex O zN a MMH Il HN OH COCH2-'N s01 l H 45 01s N-(CII2) NHSO, H,C-00'NH' violet11...but-trey. "NH; 4 OH HO 4e oQN-Q-Nm OzS-NH-CHz-CHr-N so: blue I l OH HzNExample 47 wherein m is one of the numbers of the series 2, 3, 4, 5

100 parts of a woolen yarn fabric are introduced into a bath at 45 C.consisting of 3000 parts of water, 2 parts of the chromium complex ofExample 45 and 5 parts of ammonium acetate. The temperature of the bathis then raised within 45 minutes to 98 C. and maintained at this levelanother minutes. A blue-grey dyeing is obtained having excellentlevelness and outstanding fastness properties.

We claim:

1. A metal complex dyestuff which has one metal atom selected from thegroup consisting of chromium and cobalt attached to two identical azodyestufi radicals and which has the formula in which: M represents saidmetal atom; E represents a cation; R represents a substituent selectedfrom the group consisting of hydrogen, chlorine, methyl, methoxy,ethoxy, nitro and acetylamino; R represents a substituent selected fromthe group consisting of hydrogen, chlorine, methyl and nitro; X is adivalent radical selected from the group consisting of oxygen and Y is adivalent radical selected from the group consisting of oxygen and NH; Zis a divalent radical attached to an aromatic nucleus of each azodyestuif radical and is selected from the group consisting of SO CO-,-CH --SO NH-, -CO-NH--, -NH-CO--CH and -SO -NH-(CH and 6 and wherein thesubstituent is attached to the right side of the formulae of saidradicals; and B is a. divalent radical selected from the groupconsisting of the azo coupled components:

( (iJHz /C=N c I G and 3 wherein the asterisk marks the position atwhich the coupling component is connected to the azo group, L is asubstituent selected from the group consisting of hydrogen, acetylaminoand methoxycarbamino, G is a substituent selected from the groupconsisting of hydrogen, methyl and chlorine, and Q is a substituentselected from the group consisting of hydrogen and chlorine.

2. A chromium complex dyestuif which has a chromium 19 29 5. Thechromium complex dyestufi 0f the formula:

C=N ..N-N-C\ Q /C N- 0 N 2 0 i 0' NlL-CO-CH -N s02 Cr Na. 0 NH-CO-CHz-N'so: OZN

C-N- --N-N-C C=Il 1 CH3 CH3 6. The cobalt complex dyestuff of theformula:

7. The cobalt complex dyestufi of the formula:

No references cited.

1. A METAAL COMPLEX DYESTUFF WHICH HAS ONE METAL ATOM SELECTED FROM THEGROUP CONSISTING OF CHROMIUM AND COBALT ATTACHED TO TWO IDENTICAL AZODYESTUFF RADICALS AND WHICH HAS THE FORMULA